CN109641264A - For the colored curable composition of increasing material manufacturing method, three-dimensional composite article and application thereof - Google Patents

For the colored curable composition of increasing material manufacturing method, three-dimensional composite article and application thereof Download PDF

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Publication number
CN109641264A
CN109641264A CN201780052377.3A CN201780052377A CN109641264A CN 109641264 A CN109641264 A CN 109641264A CN 201780052377 A CN201780052377 A CN 201780052377A CN 109641264 A CN109641264 A CN 109641264A
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China
Prior art keywords
weight
dyestuff
curable compositions
curable
methyl
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CN201780052377.3A
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Chinese (zh)
Inventor
焦阿基诺·拉亚
阿德里安·埃克特
马尔特·科滕
马丁·果兹格尔
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3M Innovative Properties Co
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3M Innovative Properties Co
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Publication of CN109641264A publication Critical patent/CN109641264A/en
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C13/00—Dental prostheses; Making same
    • A61C13/0003—Making bridge-work, inlays, implants or the like
    • A61C13/0006—Production methods
    • A61C13/0013—Production methods using stereolithographic techniques
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C7/00—Patterns; Manufacture thereof so far as not provided for in other classes
    • B22C7/02—Lost patterns
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/02—Sand moulds or like moulds for shaped castings
    • B22C9/04—Use of lost patterns
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • C08K5/08—Quinones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3437—Six-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/02—Homopolymers or copolymers of esters
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C13/00—Dental prostheses; Making same
    • A61C13/08—Artificial teeth; Making same
    • A61C13/082—Cosmetic aspects, e.g. inlays; Determination of the colour
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C13/00—Dental prostheses; Making same
    • A61C13/20—Methods or devices for soldering, casting, moulding or melting
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C7/00—Orthodontics, i.e. obtaining or maintaining the desired position of teeth, e.g. by straightening, evening, regulating, separating, or by correcting malocclusions
    • A61C7/12—Brackets; Arch wires; Combinations thereof; Accessories therefor
    • A61C7/14—Brackets; Fixing brackets to teeth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Abstract

The present invention relates to one kind to be used for the colored curable composition used in increasing material manufacturing method, the composition includes curable resin composition, the curable resin composition includes radiation-curable component, photoinitiator, the dye composite comprising dyestuff D1 and dyestuff D2, the maximum light absorption that dyestuff D1 has is that the maximum light absorption in the wave-length coverage of 400nm to 530nm, shown in dyestuff D2 is in the wave-length coverage of 540nm to 650nm.The three-dimensional composite article that the invention further relates to a kind of to be obtained by handling the curable compositions in increasing material manufacturing method.

Description

For the colored curable composition of increasing material manufacturing method, three-dimensional composite article and its Purposes
Technical field
The present invention relates to one kind to be used for the colored curable composition used in increasing material manufacturing method.The curable composition Object include at least two kinds of dyestuffs, the maximum light absorption that one of dyestuff has be in the wave-length coverage of 400nm to 530nm, and And the maximum light absorption that another dyestuff has is in the wave-length coverage of 540nm to 650nm.The curable compositions are conducive to Three-dimensional article is produced with high precision.Once processing, cured composition just has substantially dark, almost black appearance.
Background technique
Increasing material manufacturing method becomes more and more popular in various technical fields (including dentistry and correction field), with In production three-dimensional article.
Curable compositions for producing three-dimensional article contain curable resin, photoinitiator, higher boiling additive and Dyestuff.
2014/078537 A1 of WO (Sun et al.) describes a kind of for producing the three-dimensional manufacture material system of dental product System.For manufacture three-dimensional dental prosthesis composition include following items mixture: (methyl) acrylate, inorganic filler, Organic filler, silicone acrylic base rubber impact modifiers, pigment and photoinitiator.
2013/153183 A2 of WO (Wachter et al.) describes a kind of for producing dental component by stereolithography Composite resin composition and method.Composite resin composition contains: a) at least one poly- reactive adhesive；B) small in wavelength The first Photoepolymerizationinitiater initiater when 400nm with absorption maximum；C) the second photopolymerization that absorption maximum is at least 400nm causes Agent；And d) wavelength be less than 400nm when the absorbent with absorption maximum, with for based on composite resin carry out dentistry Shape the SLA production of component.
2008/0287564 A1 of US (Klare et al.) describes a kind of biocompatibility low viscosity radiation-curable system Agent, for producing medical product, especially adaptability earphone, ear glue component, shell by PNP method or stereolithography method Or ear piece, wherein being transferred to facing for penetration depth by adding a small amount of anaerobism inhibitor such as phenthazine or DPPH to adjust Boundary's energy.
2014/0072712 A1 of US (Xu) describes the opaque ink being used together with three dimensional printing system, it includes Polymerizable components be that 10 weight % to 95 weight %, non-reacted wax group are divided into 3 weight % to 25 weight %.
However, without a kind of completely satisfactory in curable compositions described in the prior art.
There is still a need for a kind of improved curable compositions, can be used for producing three-dimensional article by increases material manufacturing technology.
Summary of the invention
Following problems are generally observed when producing three-dimensional article by increases material manufacturing technology:
Once producing three-dimensional article by increases material manufacturing technology, just the three-dimensional article must be removed from creation platform.
Especially, if being related to widget, often it is difficult difference structure relevant to desired three-dimensional article and institute Creation and structure required for desired three-dimensional article is supported during creation process.Prepare desired three-dimensional article and The material of support construction is identical.
Another problem is related to orientation of the three-dimensional article on creation platform during manufacturing method.In order to obtain accurately As a result, three-dimensional article generally has to have certain orientation on creation platform.
Therefore, the purpose of the present invention is to provide a kind of curable compositions, which can be by increasing material system The method of making is pocessed to produce the three-dimensional article with high surface resolution.
In addition, the three-dimensional article should have enough intensity after being pocessed in increasing material manufacturing method.
It is a further object to provide a kind of curable compositions, which can be by increasing material system Method processing is made to produce three-dimensional article, any supporting element which can be easy and produce during increasing material manufacturing method Or minor structure is detached from or separation.
Should also it is desirable that, if the precision or even small size that can easily check three-dimensional article produced also such as This, and if it is required, then allow easily to modify shape and/or surface.
It is desirable that should be desired if curable compositions can be incinerated without leaving residue.
If about the orientation of three-dimensional article there are high-freedom degree during increasing material manufacturing method, and it is desired.
By that can realize at least one of above-mentioned purpose with curable compositions described in the claims herein.
In one embodiment, the present invention is characterized in that including the colored curable combination for increasing material manufacturing method A kind of composition of object, the composition includes:
Curable resin composition, it includes radiation-curable components；
Photoinitiator；
Dye composite, it includes dyestuff D1 and dyestuff D2,
The maximum light absorption that dyestuff D1 has is in the wave-length coverage of 400nm to 530nm；
Maximum light absorption shown in dyestuff D2 is in the wave-length coverage of 540nm to 650nm.
In another embodiment, the present invention relates to a kind of production is such as herein and described in the claims curable The method of composition.
The invention further relates to it is a kind of containing herein and curable compositions described in the claims Kit of parts And barrel.
In addition, the present invention is characterized in that a kind of produce three-dimensional composite article by increases material manufacturing technology as described herein Method.
The invention further relates to a kind of being obtained according to such method or obtainable three-dimensional composite articles.
Another aspect of the present invention is related to a kind of method for producing three-dimensional casted article comprising following step:
Curable compositions as described herein are handled, in increasing material manufacturing method to obtain three-dimensional composite article；
Three-dimensional composite material article is embedded in embedded material；
The material of three-dimensional composite article is replaced, by cast material to obtain the three-dimensional casting system being embedded in embedded material Product；
Embedded material is removed from three-dimensional casted article.
Unless defined differently, otherwise for this specification, following terms should have given meaning:
" hardenable component or material " or " polymerizable components " is to be gathered in the presence of photoinitiators by radiation-induced Close any component being cured or hardened.Hardenable component may include only one, two, three or more polymerizable group Group.The typical case of polymerizable groups includes unsaturated carbon group, such as especially in the presence of in (methyl) acrylate group Vinyl groups.
" photoinitiator " is (can to start in the presence of wavelength 300nm to 700nm) in radiation, especially light or initiation can be hard Change the substance of the solidification process of composition.
" monomer " is that can aggregate into oligomer or polymer by having for chemical formula characterization to increase molecular weight Polymerizable groups (including (methyl) acrylate group) any chemical substance.The molecular weight of monomer can typically simply base It is calculated in the chemical formula provided.
As used herein, " (methyl) acryloyl " is breviary term, refers to " acryloyl " and/or " methacryl ". For example, " (methyl) acryloxy " group is breviary term, refer to acryloxy group (that is, CH2=CH-C (O)- O-) and/or methacryloyloxy group is (that is, CH2=C (CH3Any one of)-C (O)-O-).
" solidification, hardening or setting reaction " is used interchangeably, and refers to physical characteristic (such as the viscosity of wherein composition And hardness) reaction that is changed over time due to the chemical reaction between each component.
Term " dentistry or correction product ", which refers to, is ready to use in dentistry or correction field, particularly for production dental prosthesis, Any product of orthodontic device, tooth model and its component.
The example of dental articles includes corona, bridge, inlay, onlay, veneer, facing, hat, corona and bridge frame in tooth Frame, implantation material, abutment, tooth abrading block, whole dental prosthesis and its part.
The example of correction product includes bracket, buccal tube, clamping plate and button and its part.
To the harmful component of patient health and therefore dentistry or correction product should not be comprising without can from dentistry or just The component of the harmfulness and toxicity moved out in abnormal product.
According to Snell's law (Snell's law) (the classic law of refraction), " transparent material " allows light to pass through.Therefore, It can see picture detail through transparent material small plate.
" trnaslucent materials " allows light partial penetration to pass through, although it be not it is fully transparent, that is, the aobvious of transmitted light is shown Write volume scattering.The reciprocal property of translucence is opacity (O).O=1/T=I/I0 (T=transmission, I=permeabilization light it is strong Degree, the intensity of the light before I=infiltration).Therefore, for the opacity value for being less than about 0.9 of the 1mm thickness small plate of diameter 15mm It is considered translucent (for example, with the Color i7 device of X. Rite Inc., the U.S. (X-Rite Corporation USA) Measurement pattern: measurement mitigates contrast ratio).Opacity can measure by various modes: in the transmission, in mitigation and In mitigation using contrast ratio method.
" increasing material manufacturing " means the method for being used to prepare three-dimensional article.The example of increases material manufacturing technology is stereolithography (SLA), wherein being laid with and radiation curing continuous layer of material under the control of the computer.Product can have substantially any shape or geometry Shape, and produced by threedimensional model or other electronic data sources.Other examples of increasing material manufacturing method or technique include 3d print Brush.
" environmental condition " means the condition that composition as described herein is usually subjected in storage and treatment process.Environment item Part can for the pressure of such as 900mbar to 1100mbar, 10 DEG C to 40 DEG C of temperature and 10% to 100% relative humidity.? Usually by ambient conditions to 20 DEG C to 25 DEG C and 1000 millibars to 1025 millibars in laboratory.
If composition does not contain certain component as essential characteristic, the composition " substantially or is substantially free of " The component.Therefore, the component is not added into composition arbitrarily, or not arbitrarily by the component and other components or with The ingredient of other components combines.Composition substantially free of certain component does not usually include the component.However, for example by In the impurity contained in raw materials used, so occasionally there are a small amount of components to be inevitable.
As used herein, "one", "an", " described ", "at least one" and " one or more " be used interchangeably.Art Meaning without limitation when language "comprising" or " containing " and its version occur in the specification and in the claims.In addition, Herein, by the numberical range that endpoint is stated include all numerical value contained within the scope of this (for example, 1 to 5 comprising 1,1.5, 2,2.75,3,3.80,4,5 etc.).
Plural form, which is added, for term means that the term should include odd number and plural form.For example, term " additive " Mean a kind of additive and more kinds of additives (for example, 2,3,4 kind etc.).
Unless otherwise specified, the amount of expression composition used in the specification and claims, as described below All numbers of the measurement of physical property etc. should be understood as being modified by term " about " in all cases.
Term " includes " should also include term " substantially by ... form " and " by ... form ".
Detailed description of the invention
Fig. 1 shows an embodiment of the printing sample according to the present invention obtained by curable compositions.
The embodiment that Fig. 2, Fig. 3 and Fig. 4 show the printing sample obtained by comparable curable compositions.
Specific embodiment
Curable compositions as described herein provide many advantageous features.
Curable compositions have specific coloring, and are very suitable for printing by increasing material manufacturing method such as SLA and add With processing.
It has also been discovered that curable compositions can be pocessed in increasing material manufacturing method, what which used Wavelength be in the range of 365nm to 405nm, this with for carrying out the manufacturing method (for example, whether it is digital light processing side Method (" DLP ") or cleaning piece method, that is, use scraper method) device it is unrelated.
Therefore, curable compositions as described herein can be solid using light substantially in any kind of increasing material manufacturing equipment Change is pocessed.
Due in curable compositions be not present inorganic colored pigments and/or inorganic filler, curable compositions and It is completely inflammable by its three-dimensional article produced.That is, pouring later may be negatively affected by not leaving after burning-up process Any residue of casting method (so-called " lost wax method " or " casting method ").
In addition, the curable compositions are convenient for creation precision architecture, i.e., since it includes the particular compositions of different dyes Make be small structure (such as in each dimension have lower than 10mm size.
The particular composition of different dyes allows to control light (especially UV light) and penetrates into curable and cured combination In object.By doing so, the cured risk of transition solidification or unwanted areas of curable compositions can be reduced.
In particular, it has been found that (methyl) acrylate based resin composition of the UV light curable of dark purple chromatic colorant is available In the accurate three-dimensional printed article of production.In solid state, printed matter seems with black surface.
If structure that is small and being decorated with metallized thread should be produced, this is especially useful.For example, for lingual bracket Increasing material manufacturing, curable compositions must satisfy particular/special requirement.
Due to being important in high precision, in this process, it is usually vital that product is visually inspected after printing.
One important method and step is to be manually removed or separate supporting element geometry from desired three-dimensional article.
Because orthodontic bracket usually has metallic yarn structure, the common 3D printing resin for hot investment casting is for small Path length (for example, if printing thin thin portion) seems substantially transparent.
Therefore, in many cases, practitioner be difficult to differentiate between whether correctly remove supporting element geometry or whether There are other artifacts.
Curable compositions as described herein solve the problems, such as this.Three-dimensional article obtained is dark color, and is being printed Black is even also substantially appeared as in thin layer later.
This is conducive to visually inspect three-dimensional article and removes support construction and unexpected artifact.
In addition, not only can easily visual detection to remaining printing artifact or support construction element, Er Qieke Easily for example forming, milling, mill or polishing by way of from three-dimensional article remove.It has been observed that raw by removing method The dust of production is brighter than the lower surface of three-dimensional article.Therefore, practitioner can easily determine to three-dimensional object surfaces which It is partially completed removing method.It has been found that this effect can be enhanced if reducing the granularity of dust.In the shape of three-dimensional article In the case where should being suitable for other reasons, this is also advantageous.
It has moreover been found that curable compositions as described herein for practitioner provide how in increasing material manufacturing machine (specific SLA printing machine) creation platform on to the more freedom for thering is three-dimensional article to be produced to be orientated.
Three-dimensional article can be arranged to substantially any desired orientation now, such as vertically or horizontally, without that will print The precision of brush result adversely affects unacceptable degree.This can contribute to produce more three-dimensional articles, while can be with More three-dimensional articles are arranged on creation platform.
In general, curable compositions described herein can pass through one of following characteristics or a variety of characterizations:
At 23 DEG C, viscosity is less than 200mPa*s；
For 5mm path length, light absorption in the range of 400nm to 650nm is more than 90%；
For 1mm path length, light transmittance is less than 25% or less than 20% (for daylight)；
For 10mm or bigger path length, color impression is dark color；
According to CIELCh colour system, in a transmissive mode for 5mm path length, h ° of tone of measurement for lower than 30；
If curable compositions are contacted with wet pH test paper, pH value 6-8；
Optionally, be inflammable within the temperature range of 600 DEG C to 900 DEG C or 600 DEG C to 800 DEG C and without remnants Object.
The viscosity of curable compositions should not be excessively high.Sufficiently low viscosity can be conducive to the portion that production is decorated with metallized thread Part.
Since there is no acidic components, curable compositions are substantially neutrality, i.e. pH value (if contacting with water) is logical Often in the range of 6 to 8.
Since there is no inorganic filler and pigment, so curable compositions are completely inflammable.That is, if by composition It is heated to 600 DEG C to 900 DEG C of temperature, then does not leave residue substantially.
Due to showing the dyestuff of the absorption band in visible spectrum there are at least two, so curable compositions are dark colours , i.e., it has low transparency.This is conducive to control light during printing process.However, curable compositions are not usually not Transparent.
Compared with commercially available composition, curable compositions as described herein are darker.This allows to produce For dark three-dimensional composite article.
The resin of Chemical composition that includes one or more radiation-curable components, one or more photoinitiators and dyestuff Composition, the dye composite include at least one dyestuff D1 and at least one dyestuff D2, and the optical absorption band that dyestuff D1 has is In blue/green spectral region, the optical absorption band that dyestuff D2 has is within the scope of green/yellow spectrum.In addition, dyestuff can With the other absorption band in the region UV of spectral region.
If desired, radiation-curable component can pass through one of following characteristics or a variety of characterizations:
The molecular weight having is in 170g/mol to 3,000g/mol or 200g/mol to 2,500g/mol or 300g/ In the range of mol to 2,000g/mol；
The viscosity having at 23 DEG C is 0.1 to 20Pa*s or 0.2 to 15Pa*s or 0.3 to 10Pa*s.
Low viscosity can be conducive to the production process of curable compositions, and can be conducive to contained in dissolved composition Other components.
Curable resin composition may include a part of one or more radiation-curable components as resin combination.
If desired, curable resin composition may include at least two, three kind or four kinds of different types of radiation can consolidate Change component.
Radiation-curable component generally comprises the main chain that radiation-curable part is attached or bonds.
Radiation-curable component generally comprises one or more (methyl) acrylate parts as reactive group or portion Point.
Radiation-curable component includes main chain and reactive group, and wherein radiation-curable component usually passes through following characteristics One of or a variety of characterizations:
One or more (methyl) acrylate part is carried as reactive group；
Aromatics, aliphatic series or aromatic-aliphatic part are carried in main chain；
One or more urethane ester moieties are carried optionally in main chain；
One or more hydroxyls are carried optionally in main chain.
According to an embodiment, (methyl) acrylate have free radical activity functional group, and including tool there are two Or more ethylenically unsaturated groups monomer, oligomer and polymer.
The amount of aggretion type group can be in 2 to 6 or even higher range.In many embodiments, aggretion type base The amount of group is in the range of 2 to 5 or 2 to 4.Polymerizable groups are usually (methyl) acryl group.
Tool includes diacrylate 1,2- glycol ester, diacrylate there are two the exemplary monomer of (methyl) acryloyl group 1,3- propylene glycol ester, diacrylate 1,9- nonanediol ester, diacrylate 1,12- dodecanediol ester, diacrylate 1,4- fourth two Alcohol ester, diacrylate 1,6-HD ester, butanediol diacrylate, bisphenol a diacrylate, diacrylate diethylene glycol (DEG) ester, Diacrylate triglycol ester, diacrylate tetraethylene glycol ester, diacrylate tripropylene glycol ester, polyethyleneglycol diacrylate, Polypropyleneglycol diacrylate, polyethylene/polypropylene copolymers diacrylate, polybutadiene two (methyl) acrylate, third The ester modified caprolactone of three (methyl) glycerol acrylates and neopentyl glycol hydroxy new pentane acid ester diacrylate of oxygroup.
There are three tools or the exemplary monomer of four (methyl) acryloyl groups includes but is not limited to trimethylolpropane tris Acrylate (such as can be with trade name TMPTA-N from the Qing Te industrial group (Cytec of State of Georgia, US Shi Maina Industries, Inc. (Smyrna, GA, USA)) it is commercially available and with trade name SR-351 from Pennsylvania, America angstrom gram This Sartomer (Sartomer (Exton, PA, USA)) is commercially available), pentaerythritol triacrylate (such as can be with Trade name SR-444 is commercially available from Sartomer (Sartomer)), ethoxylation (3) trimethylolpropane trimethacrylate (for example, can be commercially available from Sartomer (Sartomer) with trade name SR-454), ethoxylation (4) pentaerythrite 4 third Olefin(e) acid ester (for example, can be commercially available from Sartomer (Sartomer) with trade name SR-494), three (2- ethoxy isocyanide ureas Acid esters) triacrylate (for example, can be commercially available from Sartomer (Sartomer) with trade name SR-368), pentaerythrite Triacrylate and pentaerythritol tetraacrylate mixture (for example, can with trade name PETIA (wherein tetraacrylate with The ratio of triacrylate is about 1:1) and trade name PETA-K (wherein tetraacrylate and the ratio of triacrylate are big About 3:1) it is commercially available from Qing Te industrial group (Cytec Industries, Inc.)), pentaerythritol tetraacrylate (such as Can be commercially available from Sartomer (Sartomer) with trade name SR-295) and two-trimethylolpropane tetra-acrylates (such as can be commercially available from Sartomer (Sartomer) with trade name SR-355).
There are five tools or the exemplary monomer of six (methyl) acryloyl groups includes but is not limited to two season penta of five acrylic acid Four alcohol esters (for example, can be commercially available from Sartomer (Sartomer) with trade name SR-399) and six functional polyurethanes propylene Acid esters (such as commercially available from Sartomer (Sartomer) with trade name CN975).In some embodiments, radiation can Curing component is polar monomer.
As used herein, term " polar monomer " refers to the monomer with radical polymerization mould assembly group and polar group.Pole Property group be it is non-acid and generally comprise hydroxyl group, primary amido groups, secondary amido groups, tertiary amido groups, Amino group or ether group (that is, the alkylidene comprising at least one formula-R-O-R--oxygroup-alkylidene group group, wherein Each R is the alkylidene with 1 to 4 carbon atom).
Suitable optional polar monomer with hydroxyl group includes but is not limited to: hydroxyalkyl (methyl) acrylate (for example, 2- ethoxy (methyl) acrylate, 2- hydroxypropyl (methyl) acrylate, 3- hydroxypropyl (methyl) acrylate and 4- hydroxyl fourth Base (methyl) acrylate) and hydroxyalkyl (methyl) acrylamide (for example, 2- ethoxy (methyl) acrylamide or 3- hydroxypropyl Base (methyl) acrylamide), ethoxy (methyl) acrylate of ethoxylation (for example, can with trade name CD570, CD571 and List CD572 commercially available from the Sartomer (Sartomer (Exton, PA, USA)) of Pennsylvania, America Exton Body) and aryloxy group replace hydroxyalkyl (methyl) acrylate (for example, 2- hydroxyl -2- phenoxy propyl (methyl) acrylic acid Ester).
Exemplary polar monomer containing primary amido groups includes (methyl) acrylamide.Example containing secondary amido groups Property polar monomer includes but is not limited to: N- alkyl (methyl) acrylamide, such as N- methyl (methyl) acrylamide, N- ethyl (methyl) acrylamide, N- isopropyl (methyl) acrylamide, N- t-octyl (methyl) acrylamide and N- octyl (methyl) third Acrylamide.Exemplary polar monomer with tertiary amido groups includes but is not limited to: N- caprolactam, N- ethylene Base -2-Pyrrolidone, (methyl) acryloyl morpholine and N, N- dialkyl group (methyl) acrylamide, such as N, N- dimethyl (methyl) acrylamide, N, N- diethyl (methyl) acrylamide, N, bis- fourth of N- dipropyl (methyl) acrylamide and N, N- Base (methyl) acrylamide.
Polar monomer with amino group includes various (methyl) acrylic acid N, N- dialkyl aminoalkyl esters and N, N- Dialkyl aminoalkyl (methyl) acrylamide.Example includes but is not limited to: (methyl) acrylic acid N, N- dimethylamino ethyl ester, N, N- dimethyl aminoethyl (methyl) acrylamide, (methyl) acrylic acid N, N- dimethylamino propyl ester, N, N- dimethylamino Base propyl (methyl) acrylamide, (methyl) acrylic acid N, N- diethylamino ethyl ester, N, N- diethylamino ethyl (methyl) Acrylamide, (methyl) acrylic acid N, N- diethylamino propyl ester and N, N- diethyl amino propyl (methyl) acrylamide.
The illustrative polar monomer with ether includes but is not limited to: alkoxylated (methyl) alkyl acrylate, Such as (methyl) ethoxyethoxy ethyl acrylate, (methyl) acrylic acid 2- methoxy acrylate and (methyl) acrylic acid 2- ethoxy Base ethyl ester；And poly- (alkylene oxide) (methyl) acrylate, such as poly- (ethylene oxide) (methyl) acrylate and poly- (epoxy third Alkane) (methyl) acrylate.Poly- (epoxyalkane) acrylate commonly referred to as poly- (aklylene glycol) (methyl) acrylate. These monomers can have any suitable end group, such as hydroxyl group or alkoxy base.For example, when end group is methoxy group When, monomer is referred to alternatively as methoxyl group poly(ethylene glycol) (methyl) acrylate.
Workable is suitable for that (methyl) alkyl acrylate can have the alkyl group containing linear, branch or cyclic structure. The example of suitably (methyl) alkyl acrylate includes but is not limited to: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid n-pentyl ester, (methyl) acrylic acid 2- methylbutyl butenoate, (methyl) the just own ester of acrylic acid, (methyl) acrylate Ester, (methyl) acrylic acid 4- methyl -2- amyl ester, (methyl) 2-EHA, the own ester of (methyl) acrylic acid 2- methyl, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid 2- monooctyl ester, the different nonyl ester of (methyl) acrylic acid, (methyl) isoamyl acrylate, (methyl) acrylic acid 3,3,5- trimethylcyclohexyl, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, (methyl) Isodecyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid 2- Propylheptyl, the different tridecane of (methyl) acrylic acid Base ester, (methyl) acrylic acid iso stearyl ester, (methyl) octadecyl acrylate, (methyl) acrylic acid 2- octyl last of the ten Heavenly stems ester, (first Base) dodecylacrylate, (methyl) lauryl acrylate and (methyl) acrylic acid heptadecane base ester.
The methacrylate mentioned in US 4,795,823, such as bis- [3 [4]-methacryls-oxygroup can also be used Methyl -8 (9)-tricyclic [5.2.1.02,6] decyl methyl triglycol ester.
Be particularly suitable be 2,2- bis- -4 (3- methacryloxy -2- hydroxy propyloxy group) phenyl-propane (Bis-GMA), 2,2- bis- -4 (3- methylacryloyl-oxygroup propoxyl group) phenyl-propane, triethylene glycol dimethacrylate (TEGDMA) and Double methylol tricyclic-(5.2.1.02,6) silane two (methyl) acrylate.
Radiation-curable component usually exists with following amounts:
Lower limit is at least 50 weight % or at least 60 weight % or at least 70 weight %；
The upper limit is at most 98 weight % or at most 95 weight % or at most 90 weight %；
Range: 50 weight % to 98 weight % or 60 weight % to 95 weight % or 70 weight % to 95 weight %.
Weight % is for the amount of curable compositions.
The adhesive composition being described herein can also include photoinitiator.
Or unless desired result can not achieve, it is otherwise not particularly limited the property and structure of photoinitiator.
Photoinitiator by one of following characteristics or a variety of can usually characterize:
The optical absorption band shown is in the wave-length coverage of 300nm to 450nm；
At 23 DEG C, the solubility in curable compositions is at least 2g/l.
Photoinitiator usually absorbs the light in blue spectral range, such as in the range of 300nm to 450nm.The range It is usually Chong Die with the additional absorption range of dyestuff D1 and/or dyestuff D2.
Photoinitiator should dissolve in the radiation-curable component and/or hereafter of curable resin composition as described herein In the higher boiling additive further described.
Photoinitiator can generate the freedom for polymerization when being exposed to luminous energy of the wavelength between 300nm to 450nm Base.
The photoinitiator of following types can be used:
A) two components system, wherein free radical is generated and extracting hydrogen atom from compound donator；
B) components system, two of them free radical is by being cracked to form.
α diketo is usually contained according to the example of the photoinitiator of type (a), such as selected from benzophenone, xanthone Or the combined part of quinone and aliphatic amine.
It is usually contained according to the example of the photoinitiator of type (b) selected from benzoin ether, acetophenone, benzoyl oxime or acyl group The part of phosphine.
Suitable system is described in such as US 4,071,124 and WO 2009/151957.These bibliography Content is hereby incorporated herein by.
The type of photoinitiator being particularly suitable includes the type of acylphosphine oxide, such as example in US 4,737,593 It is described.Such acylphosphine oxide has general formula
(R9)2- P (=O)-C (=O)-R10
Wherein each R9It can be individually hydrocarbyl group such as alkyl, naphthenic base, aryl and aralkyl, any of them base Group can be replaced by halogen, alkyl or alkoxy base or two R9Group, which can be engaged, forms ring with phosphorus atoms, and Wherein R10It is hydrocarbyl group, five yuan comprising S, O or N or hexa-member heterocycle group or-Z-C (=O)-P (=O)-(R9)2Group, Wherein Z represents bivalent hydrocarbon radical group, such as alkylene or phenylene with 2 to 6 carbon atoms.
Preferred acylphosphine oxide is wherein R9And R10Group is phenyl or low alkyl group or the substituted benzene of lower alkoxy- Those of base." low alkyl group " and " lower alkoxy " means this kind of group with 1 to 4 carbon atom.
Exemplary ultraviolet initiator includes 1- hydroxycyclohexyl phenyl ketone (for example, with trade name " IRGACURE 184 " Derived from New York Ta Lidun the different chemical company of vapour Bart (Ciba Specialty Chemicals Corp., Tarrytown, NY)), 4- (2- hydroxyl-oxethyl) phenyl-(2- hydroxyl -2- propyl) ketone is (for example, with trade name " IRGACURE 2529 " derived from the different chemical company of vapour Bart (Ciba Specialty Chemicals Corp.)), 2- hydroxy-2-methyl benzene Acetone is (for example, derive from the different chemical company of vapour Bart (Ciba Specialty with trade name " DAROCURE D111 " Chemicals Corp.)) and bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides (for example, with trade name " IRGACURE 819 " derive from the different chemical company of vapour Bart (Ciba Specialty Chemicals Corp.)).
Most preferably, acylphosphine oxide is bis- (2,4,6- trimethylbenzoyl) phenyl phosphine oxide (IRGACURETM819, The Ciba Specialty Chemicals (Ciba Specialty Chemicals, Tarrytown, NY) of New York Ta Lidun).
Tertiary amine reducing agents can be applied in combination with acylphosphine oxide.Illustrative tertiary amine includes 4- (N, N- dimethylamino) Ethyl benzoate and N, N- dimethylaminoethyl methacrylate.
The commercially available oxygen of free radical initiation can occur when irradiating at the wavelength greater than 400nm to 1200nm Changing phosphine photoinitiator includes that bis- (2,6- Dimethoxybenzoyl) -2,4,4- tri-methyl-amyls that weight ratio is 25:75 aoxidize Mixture (the IRGACURE of phosphine and 2- hydroxy-2-methyl -1- phenyl propyl- 1- ketoneTM1700, Ciba Specialty Chemicals (Ciba Specialty Chemicals)), 2- benzyl -2- (N, N- dimethylamino) -1- (4- morpholino phenyl) -1- butanone (IRGACURETM369, Ciba Specialty Chemicals (Ciba Specialty Chemicals)), bis- (η 5-2,4- cyclopentadiene -1- Base)-bis- (the fluoro- 3- of 2,6- bis- (1H- pyrroles -1- base) phenyl) titanium (IRGACURETM784DC, Ciba Specialty Chemicals (Ciba Specialty Chemicals)), weight ratio is bis- (2,4, the 6- trimethylbenzoyl) phenyl phosphine oxides and 2- hydroxyl of 1:1 Base-2- methyl-1-phenyl propyl- 1- ketone mixture (DAROCURTM4265, Ciba Specialty Chemicals (Ciba Specialty Chemicals)) and ethyl -2,4,6- trimethyl benzyl phenyl phosphinic acid salt (LUCIRINTMLR8893X, North Carolina The BASF AG (BASF Corp., Charlotte, NC) of state Xia Luote).
Also available is comprising α, tri- keto moiety of β or the photoinitiator comprising α diketo dialkyl group ketal moieties.
Photoinitiator usually exists with following amounts:
Lower limit amount is at least 0.01 weight % or at least 0.05 weight % or at least 0.1 weight %；
Upper limit amount is at most 5 weight % or at most 3 weight % or at most 2 weight %；
Range is 0.01 weight % to 5 weight % or 0.01 weight % to 3 weight % or 0.01 weight % to 2 weights Measure %；
Weight % is for the weight of entire composition.
Curable compositions as described herein include organic dye compositions.The dye composite includes at least two different Dyestuff D1 and D2.
It has been found that using the specific dye combinations facilitate inhibit or reduce scattering light it is saturating in curable compositions It penetrates.This typically facilitates the precision or detail resolution for improving the product surface obtained by increasing material manufacturing method.
Organic dyestuff be typically free of except alkaline metal ions (such as Li, Na, K), alkaline-earth metal ions (such as Mg, Ca), the element or ion except C, N, O, H, S, P, halogen (F, Cl, Br).That is, organic dye molecule be typically free of it is any heavy Metal ion (for example, there is the metal ion for being higher than 40 or the atomic mass higher than 45).
The dyestuff that can be used includes selected from azo group and/or aromatics (miscellaneous) ring or other bodies with delocalizedπelectron Those of part of system dyestuff.Especially, it is useful that discovery, which can be used for dyeing the dyestuff of food,.
The maximum light absorption that dyestuff D1 has is in the wave-length coverage of 400nm to 530nm.
If desired, dyestuff D1 by least one of following characteristics or a variety of can be characterized:
The optical absorption band shown is in the wave-length coverage of 300nm to 450nm；
Molecular weight is 50g/mol to 1,000g/mol；
At 23 DEG C, the solubility in curable compositions is at least 0.1g/l；
It is inflammable within the temperature range of 600 DEG C to 900 DEG C and without residue；
It include anthraquinone moiety, azo moiety, naphtho- quinolyl dione part or xanthone part.
Therefore, the optical absorption band that dyestuff 1 has can also be in the wave-length coverage of 300nm to 450nm, i.e., in the region UV It is interior.
This absorption can be advantageous, because of its transmitting band substantially with the light of the device for increases material manufacturing technology Corresponding or overlapping.
It was found that the group of the light absorption in region 300nm to 450nm and 450nm into 650nmnm be combined into it is particularly useful.
In general, dyestuff D1 shows the optical absorption band in electromagnetic spectrum same range, wherein photoinitiator also shows that light absorption.
Dyestuff D1 is usually soluble in organic solvent, and is also dissolved in curable resin composition.
According to an embodiment, dyestuff D1 includes anthraquinone moiety and therefore may be characterized as anthraquinone dye.
According to an embodiment, dyestuff D1 includes azo moiety and therefore may be characterized as azo dyes.
According to an embodiment, dyestuff D1 includes naphtho- quinolyl dione part and therefore may be characterized as naphtho- quinoline two Ketone dyes.
According to an embodiment, dyestuff D1 includes xanthone part and therefore may be characterized as xanthene ketone dyes.
According to an embodiment, dyestuff D1 includes isoquinoline moiety and therefore may be characterized as isoquinolin dyestuff.
The suitable examples of dyestuff D1 are C.I. solvent red 111 (for example, SolvapermTMRed PFS；CAS 82-38-2).
Other suitable examples of dyestuff D1 include solvent red 168 (CAS 71832-19-4, anthraquinone dye), solvent red 49 (CAS 509-34-2, xanthene ketone dyes), solvent red 140 (CAS 15905-32-5, xanthene ketone dyes), pigment red 112 (CAS 6535-46-2, azo dyes), pigment red 149 (CAS 4948-15-6, perylene dyes), (the CAS 6368- of solvent red 19 72-5, azo dyes), solvent red 23 (CAS 85-86-9, azo dyes), solvent red 24 (CAS 85-83-6, azo dyes), Solvent red 26 (CAS 4477-79-6, azo dyes), solvent red 27 (CAS1320-06-5, azo dyes), 43 (CAS of solvent red 15086-94-9, xanthene ketone dyes), solvent red 52 (CAS 81-39-0, two ketone dyes of isoquinolin) and its mixture.
Dyestuff D1 usually exists with following amounts:
Lower limit is at least 0.01 weight % or at least 0.04 weight % or at least 0.08 weight %；
The upper limit is 1 weight % of 0.1 weight % of maximum or 0.5 weight % of maximum or maximum；
Range is 0.01 weight % to 1 weight % or 0.04 weight % to 0.5 weight % or 0.08 weight % to 0.1 weight Measure %；
Weight % is for the weight of curable compositions.
Maximum light absorption shown in dyestuff D2 is in the wave-length coverage of 540nm to 650nm.Therefore, dyestuff D2 absorbs light Green yl moiety (such as light of the 500nm into 650nm) of spectrum.
If desired, dyestuff D2 by least one of following characteristics or a variety of can be characterized:
The optical absorption band shown is in the wave-length coverage of 300nm to 450nm；
Molecular weight is 50g/mol to 1,000g/mol；
At 23 DEG C, the solubility in curable compositions is at least 0.05g/l；
Optionally lower than 800 DEG C at a temperature of be inflammable and without residue；
It include anthraquinone moiety, azo moiety or triphenyl methane moiety.
That is, the optical absorption band that dyestuff 2 has can also be in the wave-length coverage of 300nm to 450nm, i.e., in the region UV.
This absorption can be advantageous, because of its transmitting band substantially with the light of the device for increases material manufacturing technology Corresponding or overlapping.
It was found that the group of the light absorption in 300nm to 450nm and 500nm into the region 650nm be combined into it is particularly useful.
According to another embodiment, light absorption shown in dyestuff D2 be in the wave-length coverage of 300nm to 400nm, Intensity and light absorption are that the intensity in the wave-length coverage of 540nm to 650nm is comparably at least 20%.
Dyestuff D2 is usually soluble in organic solvent, and is also dissolved in curable resin composition.
According to an embodiment, dyestuff D2 includes anthraquinone moiety and therefore may be characterized as anthraquinone dye.
According to an embodiment, dyestuff D2 includes azo moiety and therefore may be characterized as azo dyes.
According to an embodiment, dyestuff D2 includes triphenyl methane moiety and therefore may be characterized as triphenyl methane dye Material.
According to an embodiment, dyestuff D2 includes phenoPiperazine part and it therefore may be characterized as phenoPiperazine dyestuff.
The suitable examples of dyestuff D2 are C.I. solvent violet 13 (for example, MacrolexTMViolett B, CAS 81-48-1).
Other suitable examples of dyestuff D2 include C.I. solvent blue 97, solvent blue 35 (CAS17354-14-2, anthraquinone dye Material), solvent blue 36 (CAS14233-37-5, anthraquinone dye), solvent blue 58 (CAS 29887-08-9, anthraquinone dye), solvent blue 59 (CAS 6994-46-3, anthraquinone dyes), solvent blue 97 (CAS 32724-62-2, anthraquinone dye), solvent blue 19 28 (CAS18038-99-8, anthraquinone dye), mordant indigo plant 14 (CAS1562-90-9, phenoPiperazine dyestuff), cyanine (CAS1562-85- 2, phenoPiperazine dyestuff), disperse violet 26 (CAS 6408-72-6, anthraquinone dye), solvent purple 8 (CAS 52080-58-7, triphen first Alkane dyestuff), solvent violet 14 (CAS 8005-40-1, anthraquinone dye), solvent violet 38 (CAS 68239-76-9, anthraquinone dye) and Its mixture.
Dyestuff D2 usually exists with following amounts:
Lower limit is at least 0.01 weight % or at least 0.02 weight % or at least 0.04 weight %；
The upper limit is 1 weight % of 0.1 weight % of maximum or 0.5 weight % of maximum or maximum；
Range is 0.01 weight % to 1 weight % or 0.02 weight % to 0.5 weight % or 0.04 weight % to 0.1 weight Measure %；
Weight % is for the weight of curable compositions.
In curable compositions the ratio of dyestuff D1 and dyestuff D2 be generally in the range of relative to weight 0.1:1 to 3:1 or 0.25:1 to 3:1 or 1:1 to 3:1 or 1:1 to 2:1 or 1.1:1 to 3:1.
According to an embodiment, compared with dyestuff D2, excessive dyestuff D1 is used.
It was found that this ratio is advantageous, because it allows more easily to adjust the desired color of curable compositions.
Curable compositions as described herein also may include one or more additives, including higher boiling additive, stabilization Agent or their mixture.
According to an embodiment, may be used also for the curable compositions used in increasing material manufacturing method as described herein Include one or more higher boiling additives.
Unless desired result can not achieve, it is otherwise not particularly limited the property and structure of higher boiling additive.
In certain embodiments, higher boiling additive can be by least one of parameters described below or multiple, sometimes All characterize:
Boiling point is more than 100 DEG C or more than 200 DEG C or more than 250 DEG C or more than 300 DEG C；
Molecular weight is 100g/mol to 500g/mol or 150g/mol to 450g/mol or 200g/mol to 400g/ mol；
Viscosity is 0.1mPa*s to 50mPa*s or 0.2mPa*s to 10mPa*s or 0.3mPa*s to 5mPa*s (23 ℃)；
With radiation-curable component miscibility.
Higher boiling additive using boiling point higher than 100 DEG C or higher than 200 DEG C or higher than 250 DEG C or higher than 300 DEG C can To be conducive to the mixed process of curable compositions.
It can be advantageous using the higher boiling additive of the molecular weight with above range and/or viscosity, because it can Facilitate the viscosity of adjusting curable compositions.
In addition, if three-dimensional article obtained is used to produce another kind by casting method as described below Three-dimensional article then can contribute to promote burnout using higher boiling additive.
According to an embodiment, higher boiling additive is usually that alcohol or glycol or polyglycols, monoether glycol or monoether are poly- Glycol, diether glycol or diether polyglycols, ether-ether glycol or ether-ether polyglycols, carbonate, ester or polycaprolactone.Organic higher boiling Additive usually has one or more polar groups.Organic higher boiling additive does not have polymerizable groups；That is, organic high boiling Point additive is free of the group that can undergo free radical polymerization.In addition, the component of higher boiling additive medium, which does not have, can undergo certainly The polymerizable groups being polymerize by base.
Suitable ethylene glycol or polyethylene glycol, ethylene glycol mono-ether or polyethylene glycol monoether, ethylene glycol diether or polyethylene glycol Diether and glycol ether ester or polyethylene glycol ether-ether usually have following formula:
R1O-(R2O)n-R1
In above-mentioned formula, each R1It independently is hydrogen, alkyl, aryl or acyl group.Suitable alkyl usually has 1 to 10 Carbon atom, 1 to 6 carbon atom or 1 to 4 carbon atom.Suitable aryl group usually has 6 to 10 carbon atoms, and leads to Often it is phenyl or is the phenyl replaced by alkyl with 1 to 4 carbon atoms group.Suitable carboxyl groups usually has formula- (CO)Ra, wherein RaFor with 1 to 10 carbon atom, 1 to 6 carbon atom, 1 to 4 carbon atom, 2 carbon atoms or 1 carbon original The alkyl of son.Acyl group is usually acetyl group (i.e.-C (O) CH3).In above-mentioned formula, each R2Usually alkylidene group, such as Ethylene or propylene.Variable n is at least 1, and can be in the range of 1 to 10,1 to 6,1 to 4 or 1 to 3.
The glycol or polyglycols of above-mentioned formula have two R equal to hydrogen1Group.The example of glycol includes but is not limited to second two Alcohol, propylene glycol, diethylene glycol (DEG), dipropylene glycol, triethylene glycol and tripropylene glycol.
The monoether glycol or monoether propylene glycol of above-mentioned formula have the first R equal to hydrogen1Group and equal to alkyl or aryl 2nd R1Group.The example of monoether glycol or monoether polyglycols includes but is not limited to: ethylene glycol monohexylether, ethyleneglycol monophenylether, Propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diglycol monotertiary oneself Ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, triethylene glycol monomethyl ether, triethylene glycol list ether, three Ethylene glycol monobutyl ether, Tripropylene glycol monomethyl Ether and Tri(propylene glycol)butyl ether,mixture of isomers.
The diether glycol or diether polyglycols of above-mentioned formula have two R1 groups equal to alkyl or aryl.Diether glycol or The example of diether polyglycols includes but is not limited to: ethylene glycol dipropyl ether, butyl cellosolve, dipropylene glycol butyl oxide, diethylene glycol (DEG) Dimethyl ether, diethyl carbitol, triglyme, tetraethylene glycol dimethyl ether and five glymes.
The ether-ether glycol or ether-ether polyglycols of above-mentioned formula have the first R1 group equal to alkyl or aryl and are equal to acyl group The 2nd R1 group.The example of ether-ether glycol or ether-ether polyglycols includes but is not limited to: butyl glycol ether acetic acid esters, diethylene glycol (DEG) fourth Ether acetic acid ester and diethylene glycol ether acetic acid esters.
Other suitable organic higher boiling additives are the carbonate with following formula:
In above-mentioned formula, R3For hydrogen or alkyl, such as with 1 to 4 carbon atom, 1 to 3 carbon atom or 1 carbon atom Alkyl.Example includes ethylene carbonate and propene carbonate.
Polycaprolactone is also that suitably, especially molecular mass is in 200g/mol to 1,000g/mol or 300g/mol Polycaprolactone to 800g/mol or 400g/mol to 600g/mol.
Polycaprolactone is usually the reaction product of caprolactone and glycol or triol.The typical case of glycol include butanediol, Hexylene glycol, diethylene glycol (DEG).The typical case of triol includes trimethylolpropane.
The specific example of workable higher boiling additive includes: an alcohol (for example, C6To C12, including primary alconol, secondary alcohol and uncle Alcohol), polyalcohols (such as diethylene glycol ether (CarbitolTM), hexylene glycol, ethohexadiol, decanediol, dodecanediol) and its mixing Object.
Following higher boiling additives sometimes it is preferable that polyethylene glycol, polycaprolactone, 1- decyl alcohol, diethylene glycol ether and its Mixture.In some cases, suitable higher boiling additive can also include that low boiling point alcohols (is lower than 100 DEG C；As methanol, Ethyl alcohol, propyl alcohol) and its mixture or preferably same as described above higher boiling additive.
Higher boiling additive usually exists with following amounts:
Lower limit amount is 0 weight % or at least 1 weight % or at least 5 weight %；
Upper limit amount is at most 40 weight % or at most 30 weight % or at most 20 weight %；
Range is 0 weight % to 40 weight % or 1 weight % to 30 weight % or 5 weight % to 20 weight %；
Weight % is for the weight of curable compositions.
According to another embodiment, curable compositions as described herein include one or more stabilizers.
Or unless desired result can not achieve, it is otherwise not particularly limited the property and structure of stabilizer.
Stabilizer can extend the storage life of curable compositions, help to prevent undesirable side reaction, and adjust Save the polymerization process for the radiation-curable component being present in curable compositions.
One or more stabilizers are added in curable compositions to further help in and improve three-dimensional to be produced The precision or detail resolution of product surface.
In particular, it has been found that stabilizer, which is added to, can help to pass through decrease in curable compositions as described herein Or undesirable scattering effect is avoided to enhance the resolution ratio and precision of SLA method, and increase the storage of curable compositions Service life.Workable stabilizer generally comprises phenol moieties.
The specific example of workable stabilizer include: p-methoxyphenol (MOP), hydroquinone monomethyl ether (MEHQ), 2,6 di tert butyl 4 methyl phenol (BHT；Ionol), phenthazine, 2,2,6,6- tetramethyl piperidine -1- oxygroup group (TEMPO) and its mixture.
If it exists, stabilizer exists with following amounts:
Lower limit amount is at least 0.001 weight % or at least 0.005 weight % or at least 0.01 weight %；
Upper limit amount is at most 0.02 weight % or at most 0.05 weight % or at most 0.5 weight %, at most 1 weight %；
Range is 0.001 weight % to 1 weight % or 0.005 weight % to 0.05 weight %；
Weight % is for the weight of curable compositions.
Curable compositions as described herein do not include any one of following components or whole usually:
Its amount is more than 1 weight % or the filler more than 0.1 weight %；
Its amount is more than 1 weight % or the inorganic pigment more than 0.1 weight %；
Its amount is more than 1 weight % or includes the element in addition to C, H, O, N, S, P, F, Cl, Br more than 0.1 weight % Component；
Weight % is for the weight of entire composition.
Therefore, curable compositions as described herein are substantially free of any one of said components or whole.
If it exists, these components may be not completely burned off and be may cause especially with respect to then carry out The difficulty of surface accuracy in casting method (so-called " lost wax technique ").
Suitable curable compositions include following embodiments:
Embodiment 1:
The radiation-curable component of -50 weight % to 98 weight %；
The photoinitiator of -0.5 weight % to 10 weight %；
The dyestuff D1 of -0.01 weight % to 1 weight %；
The dyestuff D2 of -0.01 weight % to 1 weight %；
The higher boiling additive of -0 weight % to 20 weight %；
Weight % is for the weight of entire composition, and wherein the component is as described herein.
Embodiment 2:
The radiation-curable component of -60 weight % to 98 weight %；
The photoinitiator of -0.5 weight % to 5 weight %；
The dyestuff D1 of -0.01 weight % to 1 weight %；
The dyestuff D2 of -0.01 weight % to 1 weight %；
The higher boiling additive of -0.1 weight % to 20 weight %；
Weight % is for the weight of entire composition, and wherein the component is as described herein.
Embodiment 3:
The radiation-curable component of -70 weight % to 98 weight %；
The photoinitiator of -0.5 weight % to 3 weight %；
The dyestuff D1 of -0.01 weight % to 1 weight %；
The dyestuff D2 of -0.01 weight % to 1 weight %；
The higher boiling additive of -1 weight % to 20 weight %；
Weight % is for the weight of entire composition, and wherein the component is as described herein.
According to preferred embodiment, curable compositions as described herein include:
Radiation-curable component, it includes (methyl) acrylate part and its amount is 50 weight % to 96 weights Measure %；
Photoinitiator, it includes phosphine oxide moiety and its amount is 0.5 weight % to 10 weight %；
Dyestuff D1, it includes anthraquinone moiety and its amount is 0.01 weight % to 1 weight %；
Dyestuff D2, it includes anthraquinone moiety and its amount is 0.01 weight % to 1 weight %；
Higher boiling additive, the molecular weight having is 100g/mol to 500g/mol and amount is 1 weight % to 20 Weight %；
The curable compositions do not include:
Its amount is more than the filler of 1 weight %；
Its amount is more than the inorganic pigment of 1 weight %；
Its amount is more than the component comprising the element in addition to C, H, O, N, S, P, halogen of 1 weight %；
Weight % is for the weight of entire composition.
Curable compositions as described herein are usually produced by merging respective components and mixing them.If It needs, can be used rate blender for mixing.
Usually produced under the conditions of saving light.
Usually in a reservoir by curable compositions as described herein storage.Suitable container includes container, foil bag, filter cylinder Deng.
The volume of corresponding container is not particularly limited, but be usually in 10ml to 200,000ml or 500ml to 10, In the range of 000ml.
Curable compositions as described herein are alternatively arranged as the component reagent comprising curable compositions and operation instructions Box provides.
Operation instructions should use curable compositions under the conditions of which is generally described in.
The invention further relates to a kind of method for producing three-dimensional composite article, this method is included in increasing material manufacturing method especially It is the step of curable compositions as described herein are processed into building material by stereolithography.
Such method generally includes following step:
Layers of build material is provided on the surface；
Layers of build material will be belonged into the solidification of those of three-dimensional article to be produced partial radiation；
Additional configurations material layer is provided to contact with the radiation-curable surface of previous layer；
The step of repeating front is until obtaining three-dimensional article.
Such method includes the steps that the surface for being applied to radiation adjustable curing material will be radiated, wherein radiation is applied only to table Those of face part will be subsequently formed a part of product to be produced.
Radiation can be applied by using such as laser beam or by mask image projection.Using based on mask image projection Stereolithography method (MIP-SL) sometimes preferably as it allows article of manufacture more quickly.
MIP-SL method can be described as follows:
I., the three-dimensional digital model of product to be produced is provided；
Ii. three-dimensional digital model is cut by one group of horizontal plane；
Iii. each slice is converted into two-dimensional mask image；
Iv. mask images are projected followed by radiation source and is located at creation platform (for example, having slotted shape) On radiation adjustable curing material surface；
V. only curing radiation curable materials in region in those of exposure；
Vi. the creation platform containing radiation adjustable curing material or curing material layer is mobile relative to radiation source, wherein mentioning It is contacted for the curing material layer produced in new radiation adjustable curing material layer and previous steps；
Vii. step (iv) is repeated to (vi) until forming desired product.
Mask images can be incident upon on radiation adjustable curing material, can relative to slot orientation from top to bottom or from bottom to top It carries out.
Can be advantageous using technology from bottom to top, since it is desired that less radiation adjustable curing material.
It has been found that curable compositions as described herein are used especially for adopting in mask image projection stereolithography method It is pocessed with shadow casting technique from bottom to top.
The invention further relates to three-dimensional composite articles obtained according to methods herein or obtainable.
The product by one of following characteristics or a variety of can usually characterize:
For 1mm path length, transmissivity is less than 20% or less than 15%；
At 2mm or bigger thickness degree, color impression is black；
According to CIELCh colour system, in a transmissive mode, for 5mm path length, h ° of tone of measurement for lower than 30 or lower than 28 or be lower than 25；
According to CIELCh colour system, in a transmissive mode, for 5mm path length, the chrominance C * of measurement be less than 20 or less than 18 or less than 15；
It is inflammable within the temperature range of 800 DEG C to 950 DEG C and without residue.
That is, three-dimensional composite article obtained has black.Black is essentially due to the presence of dyestuff D1 and D2 and draws It rises, which absorbs the major part of electromagnetic visible spectrum.
The black of three-dimensional composite article is conducive to visually inspect the surface of three-dimensional composite article, and also allows to be easy measurement Belong to the part of desired three-dimensional composite article and during increasing material manufacturing method by as support construction or passing through accident (such as due to light scatter) and the part produced.
It has been found that this tone value is particularly conducive to visual inspection three-dimensional article, even with from subsequent light (rear light Condition) it is also such.
The invention further relates to a kind of method for producing three-dimensional casted article, this method includes the following steps:
Curable compositions as described herein are handled, in increasing material manufacturing method to obtain three-dimensional composite article；
Three-dimensional composite material article is embedded in embedded material；
The material of three-dimensional composite article is replaced, by cast material to obtain the three-dimensional casting being embedded in embedded material Product；
Embedded material is removed from three-dimensional casted article.
Workable embedded material includes gypsum.
Workable cast material includes metal (such as gold, silver, platinum), based on any or all in elemental chromium, cobalt and molybdenum Dental alloys (such as WironitTM) and its mixture.
Such method can be used for producing the shape with dental articles, correction product or other widgets (including jewelry) Three-dimensional casted article.
Other than hot investment casting, curable compositions as described herein can also be used in the portion that preparation is used for modelling Part, in particular for prepare on the direction x, y and/or z have small size such as 0.5mm to 100mm or 0.5mm to 50mm or The three-dimensional article of 0.5mm to 10mm.
The complete disclosure of herein cited patent, patent document and publication, which is incorporated by reference, is incorporated to this Text, as being individually recited each file.Under the premise of not departing from the scope of the invention and essence, to of the invention various Modification and change will be evident to those skilled in the art.Description above, example and data are provided to this hair The preparation of bright composition, the description of purposes and method of the invention.The present invention is not limited to embodiment party disclosed herein Case.It will be appreciated by those skilled in the art that many present invention can be made without departing from the spirit and scope of the present invention optionally Embodiment.
Following embodiments are for illustrating the present invention, the range being not intended to limit the present invention.
Embodiment
Unless otherwise specified, all parts and percentages are by weight, all water is deionized water, and All molecular weight are weight average molecular weight.In addition, unless otherwise specified, all experiments are at (23 DEG C of environmental condition； 1013 millibars) under carry out.
Method
Method for measuring light transmittance
If desired, the Color i7 sphere spectrophotometer (love purchased from Michigan, USA Grand Rapids can be used Se Li company (X-Rite Inc., Grand Rapids, MI, USA)) measurement light transmittance (contrast ratio mode).
Test sample is printed with the shape of the cube of approx. dimension: edge length is 30 ± 0.5mm, with a thickness of 1 ± 0.05mm, and handle as described herein.
For measurement, spectrometer parameter are as follows: D65 working flare (light source；Daylight；6,500K) and 10 ° of scopes.White Be determined with black background as follows: for black background, sphere is closed and therefore light is not detected in Color i7 sensor.? When white (or 100%D65 light), it is necessary that in the case where there is no anything between the sphere of Color i7 and sensor It measures.In order to measure sample, sample is placed between the sphere and lens of Color i7 using sample holder.To Sample is placed directly on the hole of sphere.Transmissivity (T%) is calculated using soft Color iControl V7.5.10.
Color measuring in a transmissive mode
If desired, can be by using sphere spectrophotometer Colour i7 (purchased from Michigan, USA Grand Rapids X. Rite Inc. (X-Rite Inc., Grand Rapids, MI, USA)) measure the color transmitted.
Therefore, the configuration of the spectrophotometer Colour i7 of the method using basis for measuring light transmittance.
Test sample is printed with the shape of the cube of approx. dimension: edge length is 30 ± 0.5mm, with a thickness of 5 ± 0.05mm, and handle as described herein.
Color value L*, a*, b*, C* and h ° (tone) is calculated by Color i7 software.The calculating of these values is according to CIE standard. C* is the vector of a* and b* and the summary that can be considered them.Color position of h ° (tone) description in 360 ° of circles.About 0 ° of value indicates red.Value instruction purple between 300 ° and 360 ° or the transition between purple and red.Coloration (C*) 0 Indicate colourless object.
Method for measuring optical absorption band
If desired, (California, USA mulberry can be purchased from by using spectrophotometer Spectramax 190 The Molecular Devices Corporation (Molecular Devices LLC., Sunnyvale, CA, USA) of Ni Weier) measurement optical absorption spectra. Use more colorimetric cylinders such as 96 hole Microtest, 370 μ l transparent panel (BD biology section purchased from New Jersey Franklin lake Learn (BD Biosciences Franklin Lakes, NJ, USA)) it is used as colorimetric cylinder.The 200 μ l resin solution referred to is placed in In one of 96 colorimetric cylinders and it is put into Spectromax 190.In 1nm step, it is recorded between 200nm and 800nm Spectrum.
Viscosity
If desired, the slit with plate/conical system (1 ° of diameter 2525mm and angle) and 0.05 can be used 301 device of Physica Rheometer MCR measures viscosity.Each shear rate can be recorded at 23 DEG C (to open from 0.1 1/s Begin to 100 1/s, carried out with 50 exponential increased steps) viscosity number (Pas).For each shear rate, usually adopting Delay in 5 seconds is used before collection data.In addition, (can start at 23 DEG C in the constant shear of 10 1/s and increased temperature ramp To at 60 DEG C, carried out with 0.74 DEG C of step) under record viscosity number.Above mentioned measurement method is substantially conforming to DIN 53018- 1 standard.
Method for measuring pH value
If desired, pH value can be measured in a manner known to those skilled in the art.For example, resin dispersion can be existed In deionized water, and instrument such as Metrohm can be usedTM826.Alternatively, if resin be not it is coloured, wetting may be used The pH test paper or wetting (water) pH coupon of (water).
For measuring printing precision/visual inspection method
Three-dimensional article obtained can be visually inspected by using following proposal to measure printing precision.Use glasses binocular Magnifying glass before white background (conventional white printing paper), is examined under the magnifying power of 2.75x (Fa Fino) under normal indoor lamp Look into three-dimensional article.
Visual inspection is classified using following standards:
Grade Standard
++ All structures and each details are perfectly clear as it can be seen that contrast and/or opacity are very good.
+ All structures and details are as it can be seen that contrast and/or opacity are enough.
- Structure is as it can be seen that detail section is unobvious as it can be seen that contrast and/or opacity are too low.
-- Structure and details are unobvious as it can be seen that contrast and/or opacity deficiency.
Material
Table 1
For producing the conventional method of curable compositions
Respective components are placed in container, and under the conditions of saving light mixing and according to above-mentioned conventional method at Reason.
For producing the conventional method of three-dimensional article
Corresponding curable compositions (for example, about 20ml) are placed on S30 3D- printing machine, and (German Hai Musihaimu's is fast Fast shape company (Rapid Shape GmbH, Heimsheim, Germany)) printing slot in.
The CAD data of three-dimensional article to be printed is loaded into system.For testing the printing precision, use is a series of The CAD data of orthodontic bracket.
Parameters described below is for carrying out printing process:
In the direction z, layer is with a thickness of 50 μm；
The wavelength of LED light source is 405nm, is 50mW/cm for 11 seconds to every layer intensity2。
After printing process, three-dimensional article is removed from printing slot, clears up 5 minutes simultaneously with isopropanol in ultrasonic bath And then Otoflash G171 (German Baeyer Boulogne NK optical goods company (NK Optik GmbH, Baierbrunn, Germany in no N in))2Solidification 90 seconds after in the case where overflow.
The photo of printing sample is shown in Fig. 1 to Fig. 4.
Inventive embodiments (IE)
Comparative example (CE)
The characterization of curable compositions
Sample layer thickness IE1 CE 2 CE 3 CE 1
Color impression 2mm Black Blue It is red It is colourless
Coloration (C*) in a transmissive mode 5mm 6.5 46.8 104.1 32.5
Tone (h °) in a transmissive mode 5mm 14 306 46 112
Transmissivity (T%) 1mm 12.2 24.1 37.0 78.6

Claims (15)

1. one kind is used for the colored curable composition used in increasing material manufacturing method, the composition includes:
Curable resin composition, the curable resin composition include radiation-curable component；
Photoinitiator；
Dye composite, the dye composite include dyestuff D1 and dyestuff D2,
The maximum light absorption that dyestuff D1 has be in the wave-length coverage of 400nm to 530nm,
Maximum light absorption shown in dyestuff D2 is in the wave-length coverage of 540nm to 650nm.
2. the colored curable composition according to preceding claims, wherein dyestuff D1 or dyestuff D2 or dyestuff D1 and dyestuff The additional light absorption that D2 has is in the wave-length coverage of 300nm to 400nm, and intensity and light absorption are in 400nm to 650nm Wave-length coverage in the intensity of corresponding dyestuff be comparably at least 20%.
3. curable compositions according to any one of the preceding claims, by one of following characteristics or it is a variety of come Characterization:
Viscosity at 23 DEG C is less than 200mPa*s；
For 5mm path length, light absorption in the range of 400nm to 650nm is more than 90%；
For 1mm path length, light transmittance is less than 25%；
For 1mm or bigger path length, color impression is dark color；
If the curable compositions are contacted with wetting pH test paper, pH value 6-8；
It is optionally inflammable within the temperature range of 600 DEG C to 900 DEG C and without residue.
4. curable compositions according to any one of the preceding claims, the photoinitiator passes through in following characteristics It is one or more to characterize:
The optical absorption band shown is in the wave-length coverage of 300nm to 450nm；
At 23 DEG C, the solubility in curable compositions is at least 2g/l.
5. curable compositions according to any one of the preceding claims, dyestuff D1 by one of following characteristics or It is a variety of to characterize:
Molecular weight is 50g/mol to 1,000g/mol；
At 23 DEG C, the solubility in the curable compositions is at least 0.1g/l；
Include anthraquinone moiety, azo moiety, naphtho- quinolyl dione part, isoquinoline moiety or xanthone part.
6. curable compositions according to any one of the preceding claims, dyestuff D2 by one of following characteristics or It is a variety of to characterize:
Molecular weight is 50g/mol to 1,000g/mol；
Light absorption in wave-length coverage 300nm to 400nm, intensity and the light absorption are the wavelength in 540nm to 650nm The intensity in range is comparably at least 20%；
At 23 DEG C, the solubility in the curable compositions is at least 0.05g/l；
Include anthraquinone moiety, azo moiety, phenoPiperazine part or triphenyl methane moiety.
7. curable compositions according to any one of the preceding claims, the radiation-curable component include main chain and Reactive group, the reactive group are attached to the main chain, and the radiation-curable component passes through following (chemistry) features One of or a variety of characterize:
One or more (methyl) acrylate part is carried as reactive group；
Aromatics, aliphatic series or aromatic-aliphatic part are carried in the main chain；
One or more urethane ester moieties are carried optionally in the main chain；
One or more hydroxyls are carried optionally in the main chain.
8. curable compositions according to any one of the preceding claims, in the curable compositions dyestuff D1 with Dyestuff D2 is 0.1:1 to 3:1 relative to the ratio of weight.
9. curable compositions according to any one of the preceding claims, the curable compositions also include following groups Point one of or it is a variety of:
Higher boiling additive, it is therefore preferred to have the boiling point higher than 100 DEG C, amount are 1 weight relative to the weight of entire composition Measure % to 20 weight %；
Stabilizer, preferably its amount are 0.001 weight % to 1 weight % relative to the weight of entire composition.
10. curable compositions according to any one of the preceding claims, the curable compositions do not include following One of component is a variety of:
Its amount is more than the filler of 1 weight %；
Its amount is more than the inorganic pigment of 1 weight %；
Its amount is more than the component comprising the element in addition to C, H, O, N, S, P, halogen of 1 weight %；
Weight % is for the weight of entire composition.
11. curable compositions according to any one of the preceding claims, the curable compositions include:
The radiation-curable component of 50 weight % to 98 weight %；
The photoinitiator of 0.5 weight % to 10 weight %；
The dyestuff D1 of 0.01 weight % to 1 weight %；
The dyestuff D2 of 0.01 weight % to 1 weight %；
The higher boiling additive of 0 weight % to 20 weight %；
Weight % is for the weight of entire composition.
12. curable compositions according to any one of the preceding claims, the curable compositions include:
Radiation-curable component, the radiation-curable component includes (methyl) acrylate part and its amount is 50 weights Measure % to 96 weight %；
Photoinitiator, the photoinitiator includes phosphine oxide moiety and its amount is 0.5 weight % to 10 weight %；
Dyestuff D1, the dyestuff D1 include anthraquinone moiety and its amount is 0.01 weight % to 1 weight %；
Dyestuff D2, the dyestuff D2 include anthraquinone moiety and its amount is 0.01 weight % to 1 weight %；
Higher boiling additive, the molecular weight that the higher boiling additive has are 100g/mol to 500g/mol and its amount For 1 weight % to 15 weight %；
The curable compositions do not include:
Its amount is more than the filler of 1 weight %；
Its amount is more than the inorganic pigment of 1 weight %；
Its amount is more than the component comprising the element in addition to C, H, O, N, S, P, halogen of 1 weight %；
Weight % is for the weight of entire composition.
13. a kind of method for producing three-dimensional article, the method includes handling to be wanted according to aforementioned right by increases material manufacturing technology The step of curable compositions described in any one of asking.
14. a kind of three-dimensional composite article that method according to preceding claims obtains or obtainable, the product are logical Cross one of following characteristics or a variety of characterizations:
For 1mm path length, light transmittance is less than 20%；
At 2mm or bigger thickness degree, color impression is black；
According to CIELCh colour system, in a transmissive mode, for 5mm path length, h ° of tone of measurement is lower than 30；
According to CIELCh colour system, in a transmissive mode, for 5mm path length, the chrominance C * of measurement is less than 20；
It is inflammable within the temperature range of 800 DEG C to 950 DEG C and without residue.
15. a kind of method for producing three-dimensional casted article, the method includes the following steps:
Curable compositions according to any one of claim 1 to 12 are handled, in increasing material manufacturing method to obtain three Tie up composite article；
The three-dimensional composite material article is embedded in embedded material；
The material that the three-dimensional composite article is replaced by cast material, is poured with obtaining the three-dimensional being embedded in the embedded material Cast product；
The embedded material is removed from the three-dimensional casted article.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110799168A (en) * 2017-06-20 2020-02-14 3M创新有限公司 Radiation curable composition for additive manufacturing process
CN111471133A (en) * 2020-05-22 2020-07-31 兰州市口腔医院 Bio-based dental 3D printing light-cured resin formula

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3271155B1 (en) * 2015-03-19 2020-09-30 Dow Global Technologies LLC Method of additive manufacturing using photoregulated radical polymerization
DE102018119079A1 (en) * 2018-08-06 2020-02-06 Redios-Tec Gmbh Method for manufacturing a dental component
JP2022512964A (en) 2018-11-06 2022-02-07 ユティリティ グローバル，インコーポレイテッド How to manufacture a fuel cell and process its components
US11603324B2 (en) 2018-11-06 2023-03-14 Utility Global, Inc. Channeled electrodes and method of making
US11611097B2 (en) 2018-11-06 2023-03-21 Utility Global, Inc. Method of making an electrochemical reactor via sintering inorganic dry particles
US11761100B2 (en) 2018-11-06 2023-09-19 Utility Global, Inc. Electrochemical device and method of making
US11539053B2 (en) 2018-11-12 2022-12-27 Utility Global, Inc. Method of making copper electrode
WO2020112316A1 (en) * 2018-11-06 2020-06-04 Utility Global, Inc. System and method for integrated deposition and heating
US20220098403A1 (en) * 2018-12-05 2022-03-31 Avient Corporation Composition for protecting light sensitive materials
WO2021048733A1 (en) 2019-09-12 2021-03-18 3M Innovative Properties Company Apparatus, system, method of post-curing an article, and post-cured article
EP4079768A4 (en) 2020-01-22 2023-12-06 Mitsui Chemicals, Inc. Photocurable composition, three-dimensional molded product, and dental product
EP4210883B1 (en) * 2020-09-11 2024-02-14 3M Innovative Properties Company Investment casting compositions and methods
WO2022200873A1 (en) 2021-03-25 2022-09-29 3M Innovative Properties Company Additive manufacturing apparatus including two light engines and a light altering structure and a method of additive manufacturing a three-dimensional object
CN115873174B (en) * 2022-11-22 2023-11-10 明澈生物科技(苏州)有限公司 Two-photon 3D printing photosensitive composition

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1158854A (en) * 1995-11-24 1997-09-10 希巴特殊化学控股公司 Borate cointiators for photopolymerization
CN1382168A (en) * 1999-10-19 2002-11-27 阿克佐诺贝尔公司 Radiation curable hot melt composition and process for application thereof
CN102366818A (en) * 2011-09-23 2012-03-07 无锡市凯杰铸造有限公司 Lost foam casting method of casing of full-automatic lock for container
WO2015126666A1 (en) * 2014-02-18 2015-08-27 3M Innovative Properties Company Dental composition and use thereof
WO2015126865A1 (en) * 2014-02-18 2015-08-27 3M Innovative Properties Company Adhesive bonding composition and use thereof

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4071124A (en) 1976-08-26 1978-01-31 Price Donald L Electrical power supply method and system for open pit mining equipment
DE3443221A1 (en) 1984-11-27 1986-06-05 ESPE Fabrik pharmazeutischer Präparate GmbH, 8031 Seefeld BISACYLPHOSPHINOXIDE, THEIR PRODUCTION AND USE
DE3607331A1 (en) 1986-03-06 1987-09-10 Espe Pharm Praep (METH) ACRYLIC ACID ESTERS AND THEIR USE FOR THE PRODUCTION OF DENTAL MATERIALS
EP1203033A1 (en) 1999-08-13 2002-05-08 Deltamed Medizinprodukte GmbH Composition that hardens with visible light and use thereof
US6569373B2 (en) 2000-03-13 2003-05-27 Object Geometries Ltd. Compositions and methods for use in three dimensional model printing
US7300619B2 (en) 2000-03-13 2007-11-27 Objet Geometries Ltd. Compositions and methods for use in three dimensional model printing
DE102004050868A1 (en) 2004-10-18 2006-04-20 Dreve Otoplastik Gmbh Low-viscosity, radiation-curable formulation for the production of ear molds
EP1941322B1 (en) 2005-10-27 2018-05-30 3D Systems, Inc. Antimony-free photocurable resin composition and three dimensional article
EP2133064A1 (en) 2008-06-10 2009-12-16 3M Innovative Properties Company Initiator system containing a diarylalkylamine derivate, hardenable composition and use thereof
JP6438385B2 (en) 2012-04-11 2018-12-12 イフォクレール ヴィヴァデント アクチェンゲゼルシャフトＩｖｏｃｌａｒ Ｖｉｖａｄｅｎｔ ＡＧ Process for the production of dental components by composite resin composition and stereolithography
US9657186B2 (en) 2012-09-13 2017-05-23 3D Systems, Inc. Opaque inks and applications thereof
BR112015010983B8 (en) 2012-11-14 2021-04-13 Dentsply Int Inc method to produce a three-dimensional dental prosthesis by a 3d printer based on a dlp (digital light processor) or stereolithography method
JP6648371B2 (en) 2014-06-10 2020-02-14 株式会社リコー Ink, printed matter

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1158854A (en) * 1995-11-24 1997-09-10 希巴特殊化学控股公司 Borate cointiators for photopolymerization
CN1382168A (en) * 1999-10-19 2002-11-27 阿克佐诺贝尔公司 Radiation curable hot melt composition and process for application thereof
CN102366818A (en) * 2011-09-23 2012-03-07 无锡市凯杰铸造有限公司 Lost foam casting method of casing of full-automatic lock for container
WO2015126666A1 (en) * 2014-02-18 2015-08-27 3M Innovative Properties Company Dental composition and use thereof
WO2015126865A1 (en) * 2014-02-18 2015-08-27 3M Innovative Properties Company Adhesive bonding composition and use thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110799168A (en) * 2017-06-20 2020-02-14 3M创新有限公司 Radiation curable composition for additive manufacturing process
CN110799168B (en) * 2017-06-20 2023-06-23 3M创新有限公司 Radiation curable composition for additive manufacturing process
CN111471133A (en) * 2020-05-22 2020-07-31 兰州市口腔医院 Bio-based dental 3D printing light-cured resin formula

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